CN105849941A - Lithium-sulfur secondary battery - Google Patents

Lithium-sulfur secondary battery Download PDF

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Publication number
CN105849941A
CN105849941A CN201480068397.6A CN201480068397A CN105849941A CN 105849941 A CN105849941 A CN 105849941A CN 201480068397 A CN201480068397 A CN 201480068397A CN 105849941 A CN105849941 A CN 105849941A
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sulfur
cnt
lithium
growth
positive pole
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CN105849941B (en
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塚原尚希
福田义朗
野末竜弘
村上裕彦
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Ulvac Inc
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Ulvac Inc
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

Provided are: a lithium-sulfur secondary battery positive electrode with which carbon-nanotube sections in the vicinity of a collector can be reliably covered with sulfur, and with which an electrolyte solution can be efficiently supplied to base-end peripheries of the carbon nanotubes even if the sulfur expands in volume during electrical discharge; and a formation method for said positive electrode. This lithium-sulfur secondary battery positive electrode is provided with: a collector (P1); a plurality of carbon nanotubes (4) which are grown on a surface of the collector such that the collector-surface side serves as a base end, and such that the carbon nanotubes are oriented in a direction orthogonal to the collector surface; and sulfur (5) which covers the surface of each of the carbon nanotubes. In the lithium-sulfur secondary battery positive electrode, the density of the carbon nanotubes is not more than 40 mg/cm3.

Description

Lithium-sulfur rechargeable battery
Technical field
The present invention relates to a kind of lithium-sulfur rechargeable battery.
Background technology
Owing to lithium secondary battery has high-energy-density, so it is not only applicable to the portable set such as mobile phone and PC In Deng, it is further widely applied to hybrid vehicle, electric automobile, electric power storage accumulating system etc..As this lithium secondary battery In one, carry out the lithium-sulfur rechargeable battery of discharge and recharge by the reaction of lithium and sulfur in recent years and paid close attention to by people.
Known a kind of lithium-sulfur rechargeable battery, including: positive pole, it has the positive active material of sulfur-bearing；Negative pole, it has containing lithium Negative electrode active material；And dividing plate, its configuration between a positive electrode and a negative electrode, such as patent documentation 1.
It is known as the positive pole of this lithium-sulfur rechargeable battery, including collector body, on collector body surface with this collector body face side is Cardinal extremity is towards the multiple CNTs with the direction oriented growth of collector body surface normal, and is covered each by the surface of each CNT Sulfur (generally, the density of CNT is 60mg/cm3, the weight of sulfur is 0.7 times～3 times of carbon nanotubes), example Such as patent documentation 1.If this positive pole is applied to lithium-sulfur rechargeable battery, then electrolyte contacts the utilization so that sulfur on a large scale with sulfur Rate is improved, and therefore has outstanding discharge and recharge rate characteristic, as lithium-sulfur rechargeable battery specific capacity (Unit Weight of sulfur Discharge capacity) big.
Herein, as the method on the surface covering each CNT with sulfur, it is generally known that sulfur to be positioned in the life of CNT Long end also makes it melt, and makes the sulfur melted be spread to base end side by CNT gap to each other, but in this approach, Sulfur only concentrates near the growing end of CNT, and sulfur is not diffuse into around the cardinal extremity of CNT, there is this part not by sulfur Even if the situation that the film thickness covering or being capped sulfur is the most very thin.Further, because sulfur and lithium reaction generate Li when discharging2S, body Long-pending expansion about 80%, so the gap turn narrow that adjacent CNT is to each other, it is impossible to electrolyte is effectively provided to carbon and receives Around the cardinal extremity of mitron, therefore cannot obtain the product that discharge and recharge rate characteristic is outstanding and specific capacity is big.
Therefore, the present inventor etc. passes through and constantly carefully studies, and draws if the density of CNT be located at 40mg/cm3Below, then even with method same as described above, also effectively sulfur can be provided when making the melted diffusion of sulfur To collector body and the interface of the cardinal extremity of CNT, and, even if sulfur volumetric expansion when electric discharge, it is possible to effectively will electrolysis Liquid provides the understanding around CNT cardinal extremity.
Prior art literature
Patent documentation
Patent documentation 1: No. 2012/070184 description of International Publication
Summary of the invention
Invention to solve the technical problem that
In view of the foregoing, the problem of the present invention is to provide positive pole of a kind of lithium-sulfur rechargeable battery and forming method thereof, and it can use Sulfur reliably covers the part near the collector body of CNT, even if sulfur volumetric expansion when electric discharge simultaneously, it is possible to effectively will Electrolyte provides around CNT cardinal extremity.
Solve the means of technical problem
In order to solve above-mentioned technical problem, the lithium-sulfur rechargeable battery positive pole of the present invention includes: collector body；On collector body surface With this collector body face side for cardinal extremity towards the multiple CNTs with the direction oriented growth of collector body surface normal；And cover respectively Cover the sulfur of each carbon nano tube surface, described lithium-sulfur rechargeable battery positive pole, it is characterised in that: the density of CNT is at 40mg/cm3 Below.Additionally, the lower limit of the density of each CNT is by the range set of the specific capacity obtaining regulation.
Use the present invention, by the density of CNT is set as 40mg/cm3Hereinafter, sulfur by CNT to each other between Gap is diffused into base end side, and available sulfur reliably covers the part near the collector body of CNT.Even and if sulfur is when electric discharge Volumetric expansion, owing to adjacent CNT gap to each other is guaranteed, can provide collector body attached electrolyte effectively Nearly part, so sulfur contacts on a large scale with electrolyte.Its result is that the utilization rate of sulfur improves further, and can provide fully to sulfur Electronics match, available extra high rate characteristic, specific capacity improves the most further.
Herein, once covering near the collector body of CNT with sulfur, i.e. in positive pole, the amount of the sulfur of infiltration is many, then when electric discharge The quantitative change of the polysulfide that the reaction of sulfur and lithium is generated is many.Polysulfide is prone to dissolution in electrolyte, and once polysulfide leads to Cross electrolyte and arrive negative pole, then cannot promote charging reaction (oxidoreduction shuttle back and forth phenomenon).
Therefore, in the present invention, a length of apparent length when growing in wire from cardinal extremity to growing end with described CNT, Each CNT has sweep or wreath piece from least one from cardinal extremity to growing end, preferably by each CNT from Cardinal extremity is located in the range of 0.4～0.8 times of above-mentioned apparent length to the growing height of growing end.Adopt in this way, with past case Compare and the surface area of CNT can be made to increase, effectively polysulfide is adsorbed onto carbon nano tube surface, polysulfide can be suppressed Dissolution is in electrolyte, and then suppression polysulfide arrives negative pole.
The forming method of the lithium-sulfur rechargeable battery positive pole of the present invention, comprises: growth step, and it forms catalysis on the surface of substrate Oxidant layer, makes multiple CNT with this catalyst layer surface side for cardinal extremity towards orthogonal with catalyst layer surface in catalyst layer surface Direction oriented growth；And covering step, it makes sulfur melted diffusion from the growth side of described CNT, covers each carbon with sulfur The surface of nanotube；The forming method of described lithium-sulfur rechargeable battery positive pole, it is characterised in that: in growth step, will be formed The substrate of catalyst layer is arranged in heating furnace, imports containing hydrocarbon gas and the unstrpped gas of diluent gas in heating furnace, Carbon nano tube growth is made by thermal cvd.Adopt in this way, can reliably obtain each CNT as above from cardinal extremity to The positive pole of the growing height of growing end lithium-sulfur rechargeable battery in the range of 0.4～0.8 times of apparent length.
Accompanying drawing explanation
Fig. 1 is the generalized section of the lithium-sulfur rechargeable battery structure of embodiment of the present invention.
Fig. 2 is the generalized section that the positive pole shown in Fig. 1 amplifies display.
Fig. 3 (a)～(c) are the figures of the formation order of the lithium-sulfur rechargeable battery positive pole that embodiment of the present invention is described.
Fig. 4 (a)～(c) be make for showing the effect of the present invention invention product 1,2, the CNT of comparative product Section SEM photograph.
Fig. 5 is the chart of the experimental result (cycle characteristics of discharge capacity) illustrating the effect for confirming the present invention.
Detailed description of the invention
Referring to the drawings, the embodiment of positive pole of lithium-sulfur rechargeable battery that the present invention is described and forming method thereof.With reference to figure 1, lithium-sulfur rechargeable battery BT includes: positive pole P, and it has the positive active material of sulfur-bearing；Negative pole N, it has bearing containing lithium Pole active substance；Dividing plate S, it is arranged between this positive pole P and negative pole N；And electrolyte L (not shown), it is by this Dividing plate S keeps, and has lithium ion (Li between positive pole P and negative pole N+) electric conductivity.
As negative pole N, such as, can use the alloy of Li, Li and Al or In etc., or be doped with the Si of lithium ion, SiO, Sn、SnO2Or hard carbon.As dividing plate S, multiple aperture plasma membrane or the non-woven fabrics of the resin material such as polyethylene or polypropylene can be used.Electricity Solve liquid L comprise electrolyte and dissolve the solvent of electrolyte, as electrolyte, known double (fluoroform sulphonyl) can be used sub- Amine lithium (calling " LiTFSI " in the following text), LiPF6、LiBF4Deng.Further, as solvent, known product can be used, such as can make With from oxolane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether., tetraethylene glycol dimethyl ether, diethoxyethane (DEE), two At least one selected in the esters such as ethers, diethyl carbonate, propylene carbonate such as Ethyl Methyl Ether (DME).Further, be Make discharge curve stable, in this at least one selected, preferably mix dioxolanes (DOL).Such as, when using diethoxy When the mixed liquor of base ethane and dioxolanes is as solution, the mixing ratio of diethoxyethane and dioxolanes can be set as 9:1. Owing in addition to positive pole P, other elements can use known product, so omit detailed description thereof herein.
And include positive electrode collector P1 and the positive active material formed on positive electrode collector P1 surface with reference to Fig. 2, positive pole P Layer P2.Positive electrode collector P1 such as has substrate 1, the base that film thickness is 5～80nm formed on the surface of substrate 1 Film (also referred to as " Obstruct membrane ") 2 and the catalyst layer that film thickness is 0.5～5nm 3 formed on basement membrane 2.As Substrate 1, such as, can use the metal forming being made up of Ni, Cu or Pt or wire netting.Basement membrane 2 be for improve matrix 1 with under The product of the adaptation of the CNT 4 of literary composition, at least one metal such as can selected from Al, Ti, V, Ta, Mo and W Or the nitride of this metal is constituted.Catalyst 3 is such as made up of at least one metal selected from Ni, Fe or Co.
Positive electrode active material layer P2 is by the multiple carbon in the surface of positive electrode collector P1 court with the direction oriented growth of this surface normal The sulfur 5 on nanotube 4 and the whole surface that covers each CNT 4 is constituted.There is gap S1 to each other in CNT 4, Electrolyte (electrolyte) flows into this gap S1.As the growing method (growth step) of CNT 4, as mentioned below, Use can use the thermal cvd of heating furnace.On the other hand, the method as the surface being covered each by CNT 4 with sulfur 5 (is covered Lid step), use the growing end at CNT 4, sow granular sulfur, be heated to more than the fusing point (113 DEG C) of sulfur 5 Making sulfur 5 melt, melted sulfur 5, by CNT 4 gap S1 to each other, is diffused into base end side.
But, if the S1 that CNT 4 is to each other is narrow, then there is melted sulfur 5 cannot reliably be expanded by this gap S1 It is scattered to the situation of base end side.Further, due to during electric discharge sulfur 5 react and volumetric expansion with lithium, so narrow when gap-ratio charges, electric Solution liquid difficultly flows into.
Therefore, in the present embodiment, the density (weight of unit volume) of CNT 4 is set in 40mg/cm3Below. Additionally, the lower limit of density is set by the scope of the specific capacity that can obtain regulation.Adopt in this way, due to CNT 4 that Gap around here is guaranteed, so melted sulfur is diffused into the base end side of CNT, available sulfur covers the base of CNT Side, and, even if sulfur 5 volumetric expansion when electric discharge, electrolyte may also flow into the base end side of CNT.Use this side Method, sulfur contacts on a large scale with electrolyte, and the utilization rate of sulfur improves further, with can to sulfur provide sufficient electronics match, can Obtaining extra high rate characteristic, specific capacity improves the most further.
Herein, once cover near the collector body of CNT 4 with sulfur 5, then in positive pole P, the quantitative change of the sulfur of infiltration is many, then When electric discharge, the quantitative change of the polysulfide that sulfur 5 and the reaction of lithium are generated is many, it is easy to cause oxidoreduction to shuttle back and forth phenomenon.Therefore, As in figure 2 it is shown, a length of apparent length l when growing in wire from cardinal extremity to growing end with CNT 4, each CNT 4 There is from cardinal extremity to growing end sweep or wreath piece from least one, making CNT 4 be grown to each CNT The 4 growing height h from cardinal extremity to growing end are in the range of 0.4～0.8 times of apparent length l.Adopt in this way, due to Past case is compared and the surface area of CNT 4 can be made more to increase (such as becoming 1.3 times～2.4 times), so effectively will vulcanize Thing is adsorbed onto CNT 4 surface, and polysulfide dissolution can be suppressed in electrolyte L, and then suppression polysulfide arrives negative pole N.Additionally, if less than 0.4 times, then, in the case of making sulfur infiltrate in a large number, there is the problem that sulfur provides electric conductivity insufficient, On the other hand, if greater than 0.8 times, then there is surface area and increase insufficient problem.Hereinafter, referring also to Fig. 3, this reality is described Execute the forming method of the lithium-sulfur rechargeable battery positive pole of mode.
Form basement membrane 2 on the surface of substrate 1, form catalyst layer 3 on the surface of basement membrane 2 and make positive electrode collector P1.As Basement membrane 2 and the forming method of catalyst layer 3, such as, can use known e-beam evaporation, sputtering method and use containing urging The infusion process of the compound solution of agent metal, therefore, detailed herein.
Then, as growth step, above-mentioned collector body P1 is arranged in known heating furnace (not shown), in heating furnace Import hydrocarbon-containifirst gas and the unstrpped gas of diluent gas.As hydrocarbon gas, such as, use methane, ethylene, acetylene etc., then Have, as diluent gas, nitrogen, argon or hydrogen can be used.Further, the flow of hydrocarbon gas and diluent gas can be according to place The reason volume of room and be appropriately arranged with, the flow controllable of such as hydrocarbon gas in the range of 10～500sccm, the stream of diluent gas Amount can be set in (differential pressure now is such as set to 100Pa～atmospheric pressure) in the range of 100～5000sccm.Further, Collector body P1 in heating furnace and unstrpped gas are heated to the temperature of 600～800 DEG C.Thus, as it has been described above, each carbon nanometer Pipe 4 has sweep or wreath piece from least one from cardinal extremity to growing end, and each CNT 4 is from cardinal extremity to growth The growing height h of end is in the range of 0.4～0.8 times of apparent length l.Now the density of CNT is at 40mg/cm3Below. In the present invention, there is in the CNT 4 of at least one place's sweep or wreath piece the CNT comprising helical form growth 4.Herein, although the mechanism that CNT 4 bends or distorts might not be very clear and definite, but with reference to the enlarged drawing of Fig. 2, it is believed that Being to be caused by catalyst layer 3, the speed of growth of left part 4L of CNT 4 is faster than right part 4R, therefore its growth With the composition of left and right directions, owing to there is adjacent CNT 4, so to the side that there is broad space (free space) To bending or distortion.As the heating furnace of the local growth speed difference that can produce CNT 4 like this, can use to being arranged on The electric furnace (also referred to as " Muffle furnace " or " atmosphere furnace ") of the heater electrified regulation chamber interior volume of chamber interior or outside, poly- The light of collection infrared lamp etc. is the main image furnace carrying out and heating with heating target thing (collector body P1).
Then, as covering step, particle diameter is sowed from the upper side in 1～100 μm in the whole region of CNT 4 growth In the range of granular sulfur 51.The weight of sulfur 51 is set to 0.2 times～20 times of the weight of CNT 4.If Less than 0.2 times, then sulfur cannot the surface of each CNT of uniform fold 4, if more than 20 times, then sulfur 5 is filled into adjacent CNT gap S1 each other.Further, positive electrode collector P1 is arranged in the tube furnace outside figure, is heated to melting at sulfur The temperature of more than point (113 DEG C) 120～250 DEG C makes sulfur 51 melt.If additionally, heat in atmosphere, then the sulfur melted Generate sulfur dioxide with the reaction of moisture in air, the most preferably heat in the inert gas atmospheres such as Ar or He or in vacuum.
Herein, in the present embodiment, owing to the density of each CNT 4 is set to 40mg/cm3Hereinafter, so melted sulfur 51 flow in CNT 4 gap to each other and are reliably diffused into the cardinal extremity of CNT 4.Its result is CNT 4 Surface entirety covered by sulfur 5, there is gap S1 (with reference to Fig. 2) to each other in adjacent CNT 4.
Then, tested to confirm the effect of the present invention.In this experiment, first, just making as follows Pole P.I.e. using diameter of phi 14mm, thickness 0.020mm Ni paper tinsel as substrate 1, by e-beam evaporation on Ni paper tinsel 1 Form the Al film as basement membrane 2 that film thickness is 50nm, on Al film 2, form film thickness by e-beam evaporation For the Fe film as catalyst layer 3 of 2nm, obtain positive electrode collector P1.Then, positive electrode collector P1 is placed in heating In stove, in heating furnace, provide acetylene 100sccm and nitrogen 5000sccm, be that an atmospheric pressure, temperature are in operating pressure 750 DEG C, under conditions of growth time is 60 minutes, make CNT 4 be perpendicular to the growth of positive electrode collector P1 surface orientation.This Time CNT 4 density be 16.5mg/cm3.By configuring granular sulfur 51 on CNT 4, and place it in In heating furnace, heat 5 minutes with 250 DEG C under an ar atmosphere, make positive pole P so that sulfur 5 covers CNT 4.At this just In the P of pole, the sulfur 5 of unit are and the weight ratio of CNT 4 are 7.17 (10.27 (mg/cm2)/1.43(mg/cm2))。 Further, make using the multiple aperture plasma membrane of polypropylene material as dividing plate S, the lithium metal with a diameter of 15mm Φ, thickness as 0.6mm It is oppositely arranged in dividing plate S both sides for negative pole N, positive pole P and negative pole N, makes dividing plate S keep electrolyte L to prepare lithium sulfur secondary electricity The coin battery in pond.Herein, the electrolyte L of use is that the LiTFSI as electrolyte is dissolved into diethoxyethane (DEE) It is adjusted to the product of 2mol/l with concentration in the mixed liquor (mixing ratio 9:1) of dioxolanes (DOL).With so produce Coin battery is as invention product 1.Further, so that CNT is with 25.3mg/cm3Density growth, the most all with upper Stating the coin battery that invention product 1 makes equally is invention product 2.Further, so that CNT is with 43.4mg/cm3Density Growth, the coin battery the most all made as foregoing invention product 1 is comparative product.Fig. 4 (a)～(c) divide These invention product 1,2 and SEM photograph of comparative product are not shown.Adopt in this way, confirm the density at CNT For 40mg/cm3In invention below product 1,2, sulfur covers the base end side of CNT, on the contrary in density higher than 40mg/cm3 Comparative product in, sulfur does not covers the base end side of CNT.Further, confirm in invention product 1, CNT 4 from Cardinal extremity, to 0.6 times that the growing height h of growing end is apparent length l, is 0.9 times, in comparative product in invention product 2 It it is 0.9 times.
Then, respectively foregoing invention product 1,2 and comparative product are carried out discharge and recharge, the cycle characteristics of charge/discharge capacity such as Fig. 5 Shown in.According to this figure, confirming in invention product 1, even if being also 1000mAh/g the 37th discharge capacity, producing with invention Product 2 compare available high cycle characteristics with comparative product.This may be considered in invention product 1, CNT described above CNT 4 compared with growing height h is apparent length l 0.6 times of 4, invention product 2 with 0.9 times and comparative product Surface area is bigger, polysulfide dissolution therefore can be suppressed in electrolyte, can inhibited oxidation reduction shuttle back and forth phenomenon.
Above, embodiments of the present invention are illustrated, but the present invention is not limited in foregoing.Lithium-sulfur rechargeable battery Shape be not particularly limited, in addition to above-mentioned coin battery, it is also possible to be coin shape, flap-type, cascade type, cylindrical shape etc..
Description of reference numerals
BT ... lithium-sulfur rechargeable battery, P ... positive pole, N ... negative pole, L ... electrolyte, P1 ... collector body, 1 ... substrate, 4 ... carbon is received Mitron, h ... the growing height of CNT, l ... the apparent length of CNT, 5 ... sulfur.

Claims (3)

1. a lithium-sulfur rechargeable battery positive pole, comprising: collector body；With this collector body face side as base on collector body surface End is towards the multiple CNTs with the direction oriented growth of collector body surface normal；And it is covered each by the sulfur of each carbon nano tube surface, Described lithium-sulfur rechargeable battery positive pole, it is characterised in that:
The density of CNT is at 40mg/cm3Below.
Lithium-sulfur rechargeable battery positive pole the most according to claim 1, it is characterised in that: with described CNT from cardinal extremity to Growing end be wire growth time a length of apparent length, each CNT have from least one from cardinal extremity to growing end curved Bent portions or wreath piece, each CNT growing height from cardinal extremity to growing end is at 0.4 times～the model of 0.8 times of apparent length In enclosing.
3. a forming method for lithium sulfur secondary pond positive pole, it comprises: growth step, and it forms catalysis on the surface of substrate Oxidant layer, makes multiple CNT with this catalyst layer surface side for cardinal extremity towards orthogonal with catalyst layer surface in catalyst layer surface Direction oriented growth；And covering step, it makes sulfur melted diffusion from the growth side of described CNT, covers each carbon with sulfur The surface of nanotube；The forming method of described lithium sulfur secondary pond positive pole, it is characterised in that:
In growth step, the substrate defining catalyst layer is arranged in heating furnace, imports containing hydro carbons gas in heating furnace Body and the unstrpped gas of diluent gas, make carbon nano tube growth by thermal cvd.
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